WO2008029809A1 - Matériau creux étiré multicouche - Google Patents

Matériau creux étiré multicouche Download PDF

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Publication number
WO2008029809A1
WO2008029809A1 PCT/JP2007/067232 JP2007067232W WO2008029809A1 WO 2008029809 A1 WO2008029809 A1 WO 2008029809A1 JP 2007067232 W JP2007067232 W JP 2007067232W WO 2008029809 A1 WO2008029809 A1 WO 2008029809A1
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Prior art keywords
ethylene
modified
propylene
hollow body
weight
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PCT/JP2007/067232
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English (en)
Japanese (ja)
Inventor
Isao Wada
Hidekazu Mitsuhashi
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Prime Polymer Co., Ltd.
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Application filed by Prime Polymer Co., Ltd. filed Critical Prime Polymer Co., Ltd.
Priority to KR1020097006945A priority Critical patent/KR101029438B1/ko
Priority to CN2007800329661A priority patent/CN101511591B/zh
Priority to AU2007292139A priority patent/AU2007292139B2/en
Priority to US12/310,671 priority patent/US20090269528A1/en
Priority to JP2008533167A priority patent/JP4844852B2/ja
Publication of WO2008029809A1 publication Critical patent/WO2008029809A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a general shape other than plane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/80—Medical packaging
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]

Definitions

  • the present invention relates to a multilayer stretched hollow body including both surface layers mainly composed of a propylene-based polymer and an intermediate layer composed of an ethylene'bule compound copolymer, and more specifically, excellent transparency and gas noria.
  • the present invention relates to a multilayer stretched hollow body having one characteristic.
  • Polypropylene is used in a wide range of applications including food containers and pharmaceutical containers because it is excellent in chemical characteristics, physical characteristics, and moldability, and is inexpensive.
  • Polypropylene itself has poor gas barrier properties, so when using polypropylene as a food storage container, a method of laminating ethylene butyl alcohol copolymer (EVOH), etc., which is excellent in gas nooriety is adopted.
  • EVOH ethylene butyl alcohol copolymer
  • the adhesion between polypropylene and EVOH is poor, as a method for improving the adhesion between polypropylene and EVOH, for example, a modified polypropylene resin graft-modified with an unsaturated carboxylic acid or its derivative (such as Mitsui Chemicals Admer) Has been proposed for use as an adhesive layer (for example, Patent Document 1, Patent Document 2, and Patent Document 3).
  • a container made of polypropylene alone has a good water vapor barrier property but poor oxygen barrier property
  • a container made of polyethylene terephthalate (PET) alone has good oxygen barrier property, Since the water vapor barrier property is inferior, there is a demand for a container having both a water vapor barrier property and a good oxygen noble nature.
  • Patent Document 1 Japanese Patent Laid-Open No. 2001_58374
  • Patent Document 2 Japanese Unexamined Patent Application Publication No. 2004 82582
  • Patent Document 3 Japanese Translation of Special Publication 2002-542077 Disclosure of the invention
  • the present invention is intended to solve the problems associated with the prior art as described above, and is excellent in transparency and gas-noirality, which compensates for the shortcomings of a container made of polypropylene alone and PET alone.
  • a container made of polypropylene alone and PET alone For the purpose of providing a multilayer stretched hollow body having
  • the present invention provides a surface layer comprising a propylene polymer composition comprising a propylene polymer (I) and a modified propylene polymer (II) graft-modified with an unsaturated carboxylic acid or derivative thereof, and ethylene.
  • C weight) force / (A + B + C) ⁇ 0 multilayer stretched hollow body, which is a 05 relates.
  • the multilayer stretched hollow body of the present invention is excellent in transparency and gas barrier properties, and is excellent in appearance without delamination. Further, the multilayer stretched hollow body of the present invention has a specific gravity of about 0.9, and has a feature that it can be reduced in weight and weight by about 30% or more than conventional multilayer bottles and glass.
  • the propylene-based polymer constituting the surface layer of the multilayer stretched hollow body of the present invention is a homopolymer of propylene or a copolymer of propylene and 5% by weight or less of ⁇ -olefin.
  • a-olefin is a normal ⁇ -olefin having 2 to 10 carbon atoms other than propylene, such as ethylene, 1-butene, 3-methyl 1-butene, 1 pentene, 3-methyl-1 Mention may be made of pentene, 4-methyl-1-pentene, 1-xene, 1-octene.
  • the melt flow rate (MFR; ASTM D 1238 230 ° C 2.16 kg load) of the propylene-based polymer according to the present invention is particularly limited as long as it can be mixed with a modified propylene polymer described later and stretch blow molded. Although not limited, it is usually in the range of 0.5 60 g / 10 min, preferably 10 40 g / 10 min, more preferably 15 35 g / 10 min, still more preferably 20 35 g / 10 min.
  • the unit derived from ethylene is 0.55% by weight, more preferably 2.04.5% by weight, still more preferably 3.04.2% by weight.
  • a Ziegler-Natta catalyst or a meta-octacene catalyst which are generally used at present, can be used without limitation, but the following general formula (1
  • the meta-orthene catalyst containing a meta-orthene compound represented by) is preferably used.
  • R 1 R 2 R 3 R 4 R 5 R 6 R 10 R U R 12 R 13 R 14 is selected from hydrogen, a hydrocarbon group, and a silicon-containing group, and may be the same or different.
  • M is a Group 4 transition metal
  • Y is a carbon atom or a key atom
  • Q is a halogen, a hydrocarbon group, a gayon ligand, or a neutral ligand that can coordinate with a lone pair.
  • j is an integer from !!
  • bridged meta-cyclocene compounds include isopropylidene (3-tert-butyl-5-methyl-cyclopentagenyl) (fluorenyl) zirconium dichloride, isopropylidene (3-te rt-butyl-5-methyl-cyclohexane).
  • Pentagenyl (3,6-di tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentagenyl) (fluoreninole) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (2,7-di tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopenta Genyl) (3,6-di tert-butyl fluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-methyl cyclopentageninole) (Otamechi Noreoctahydrodibenzofunoleleninole) dinoleconium dichloride, isopropylidene (3-tert-butyl
  • the metalocene catalyst is composed of the following components (a) to (c).
  • component (a), component (b) and component (c) various components disclosed in the international application WO20 05/019283 by the applicant of the present application can be used without limitation.
  • a propylene polymer produced by using the above-mentioned meta-locene catalyst is used as the propylene polymer according to the present invention, a multilayer stretched hollow body having further excellent transparency can be obtained.
  • the modified propylene polymer constituting the surface layer of the multilayer stretched hollow body of the present invention is a polymer obtained by graft-modifying a propylene polymer with an unsaturated carboxylic acid or a derivative thereof.
  • the propylene polymer to be graft-modified may be a polymer in the same category as (I) the propylene polymer, but a propylene homopolymer is preferred!
  • Preferred examples of the unsaturated carboxylic acid or derivative thereof include maleic anhydride.
  • a modified propylene polymer trade name Admer (maleic anhydride graft polymer) manufactured by Mitsui Chemicals, Inc. can be exemplified.
  • the amount of graft polymerization of the unsaturated carboxylic acid or derivative thereof in the modified propylene polymer is preferably 0.0;! To 5% by weight, more preferably 0.3 to 5% by weight, even more preferably. Is in the range of 0.6-5% by weight.
  • the melt flow rate of modified propylene polymer (HMFR; ASTM D 1238, 230 ° C, 2.16 kg load) is not particularly limited as long as it can be mixed with the propylene polymer and stretch blow molded, but it is usually 3 g / 10 min or more, preferably 3 to 20 g / 10 min, more preferably 5 to 15 g / 10 min.
  • the amount of graft polymerization and the melt flow rate are within the above ranges as the modified propylene polymer, the dispersibility with the propylene polymer is improved, and the ethylene 'vinyl compound copolymer as an intermediate layer is obtained. This can greatly contribute to the adhesive strength with the layer and the suppression of the decrease in transparency, and a good multilayer stretched hollow body can be obtained.
  • the ethylene'bulu compound copolymer constituting the intermediate layer of the multilayer stretched hollow body of the present invention has a melt flow rate (ASTM D1238, 210 ° C, 2.16 kg load) of 8 g / 10 min or more, preferably 8-30 g / 10 minutes, more preferably in the range of 10-20 g / 10 minutes, and crystallization temperature Tc (in DSC measurement under nitrogen atmosphere, the temperature is decreased from 240 ° C to 10 ° C / min.
  • the crystallization peak temperature at the time of heating is 138 ° C or higher, preferably 140 ° C or higher and 160 ° C or lower.
  • the value of the melt flow rate of the ethylene / bulle compound copolymer is preferably smaller than the value of the melt flow rate of the (I) propylene-based polymer.
  • An ethylene-bulu compound copolymer having a melt flow rate of less than 8 g / 10 min cannot form an ethylene-bulu compound copolymer layer having a uniform thickness at the time of preform and stretched hollow molding with low fluidity, Noria uniformity is inferior. Furthermore, the ethylene'bule compound copolymer is crystallized at the time of co-injection molding with a propylene-based copolymer and the like and in the preheating process before stretch blow, the transparency of the resulting multilayer stretched hollow body is reduced, There is a risk that it will be generated. In addition, the melt fluidity with the propylene polymer and modified propylene polymer may be adversely affected, and the transparency of the resulting multilayer stretched hollow body may be greatly affected.
  • the ethylene'bulu alcohol copolymer according to the present invention is preferably an ethylene'bulualcohol copolymer, and may further be a modified ethylene'bulualcohol copolymer modified with an epoxy compound. More preferred.
  • Preferred examples of the epoxy compound include an epoxy compound constituting a structural unit represented by the following general formula (2) in a modified butyl alcohol copolymer preferably having a molecular weight of 500 or less.
  • Such a modified ethylene-butyl alcohol copolymer is excellent in stretchability and does not deteriorate the barrier properties and transparency of the resulting multilayer stretched hollow body.
  • R 1 , R 2 , R 3 and R 4 are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aliphatic hydrocarbon group having 3 to 10 carbon atoms, an alicyclic hydrocarbon group having 10 to 10 carbon atoms, Represents an aromatic hydrocarbon group having 6 to 10 carbon atoms;
  • R 2 , R 3 and R 4 may be the same group or different.
  • R 3 and R 4 are combined May be.
  • R 2 , R 3 and R 4 may have a hydroxyl group, a carboxyl group or a halogen atom.
  • the modified ethylene 'butyl alcohol copolymer is a modified ethylene' butyl alcohol copolymer in which R 1 and R 2 are both hydrogen atoms. In a more preferred embodiment, it is a modified ethylene 'butyl alcohol copolymer in which one of R 3 and R 4 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms and the other is a hydrogen atom. In another more preferred embodiment, one of R 3 and R 4 is a substituent represented by (CH 3) OH (where i is an integer of 1 to 8), and the other is a hydrogen atom It is a modified ethylene 'butyl alcohol copolymer.
  • the modification rate of the ethylene-butalcohol copolymer by the epoxy compound is preferably 0.1 to 5. Omol%, more preferably 0.5 to 2. Omol%, and still more preferably 1. 0 to; 1. Within the range of 5 mol%.
  • modified ethylene-bulcoalcohol copolymer having the above-mentioned melt flow rate and crystallization temperature and further modified with an epoxy compound is used as the modified ethylene-bulcoalcohol copolymer, it is transparent and stretched. A container without any delamination can be obtained.
  • the propylene-based polymer composition as both surface layers of the multilayer stretched hollow body of the present invention contains the propylene-based polymer (I) and the modified propylene polymer (II), and the propylene-based polymer content A ( Weight) and modified propylene polymer content B (weight) ratio is B / (A + B) ⁇ 0.15, preferably (0.15—0.40, more preferably (0.15— When the composition having a modified propylene polymer content of less than 0.15 is used as the surface layer, after the stretch blow molding, the resulting multilayer stretched hollow body is an intermediate layer of ethylene. 'It is not preferable because it easily peels off from the bull compound copolymer layer, resulting in poor appearance.
  • the propylene-based polymer composition according to the present invention may be mixed with various known additives as long as the object of the present invention is not impaired.
  • additives general nucleating agents using organophosphate esters and fatty acid metal salts as dispersants, such as Ade Riki Co., Ltd. ⁇ -21, lubricants, neutralizers and antioxidants, etc. Is mentioned.
  • additives such as a phosphorus antioxidant and a neutralizer are added as necessary, and a Henschel mixer is added.
  • the above components and additives can be obtained by melt-kneading using a single screw extruder, multi-screw extruder, kneader, Banbury mixer, etc.
  • a high-quality propylene-based polymer composition that is uniformly dispersed and mixed can be obtained.
  • the multilayer stretched hollow body of the present invention comprises both surface layers comprising a propylene polymer composition comprising a propylene polymer (I) and a modified propylene polymer ( ⁇ ⁇ ⁇ ⁇ ⁇ ) graft-modified with an unsaturated carboxylic acid or a derivative thereof. And an intermediate layer composed of an ethylene'bule compound copolymer (III) and an amount of the propylene polymer (I); A (weight) and a modification modified by grafting with the unsaturated carboxylic acid or derivative thereof The amount of propylene polymer ( ⁇ ); B (weight) is B / (A + B) ⁇ 0.15, and the melt flow rate (ASTM D1238, 210) of the ethylene-bulu compound copolymer (III).
  • a multilayer stretched hollow body characterized in that the amount of the cellulose compound copolymer (III); C (weight) is C / (A + B + C) ⁇ 0.05.
  • the ratio of the ethylene'bulu compound copolymer, which is the intermediate layer of the multilayer stretched hollow body, is within the above range, the ability to stably form the ethylene'bull compound copolymer layer in the intermediate layer. If it is less than that, it is not preferred because the ethylene / bulu compound copolymer layer may be broken after stretch blow and the gas noorality may not be maintained.
  • the thicknesses of both the surface layer composed of the propylene-based polymer composition and the intermediate layer composed of the ethylene'bulu compound copolymer in the multilayer stretched hollow body of the present invention can be determined according to various uses.
  • the multilayer stretched hollow body of the present invention may further have other layers as long as it has both the surface layer and the intermediate layer.
  • the other layer may be between both surface layers and the intermediate layer or may be laminated on one surface layer.
  • the multilayer stretched hollow body of the present invention can be produced by using a stretch blow molding machine that has at least two injection units and can be simultaneously injected into a hot runner.
  • the propylene-based polymer composition as both surface layers is injected from a main injection unit, and then a fixed amount of a modified ethylene'bule compound copolymer is injected from a sub-injection unit.
  • an intermediate layer composed of a modified ethylene'bule compound copolymer is formed to form a preform having a layer structure of three or more layers. Subsequently, if necessary, preheating is performed and stretch blow molding is performed, so that a multilayer stretched hollow body having excellent transparency and gas-noirality can be obtained.
  • Stretch blow molding is different from the hollow molding method (direct blow molding method) in that the preform is forcibly stretched longitudinally using a stretching rod, etc., and is further stretched in the longitudinal and transverse directions almost simultaneously. This is a molding method by press-fitting a pressurized fluid such as low air or nitrogen.
  • the melting and injection temperatures of the propylene-based polymer composition are usually in the range of 200 to 280 ° C.
  • the preform temperature just before stretching is about 110 to 150 ° C
  • the longitudinal stretching ratio is 1.5 to 3.0 times
  • the transverse stretching ratio is usually 1.5 to 3.0 times.
  • the body of the stretch blow container was cut out, and water permeation tests were conducted according to the JIS K7129 B method, oxygen according to the J IS K 7126 method, and carbon dioxide gas under the same pressure method. .
  • DSC differential scanning calorimeter
  • each sample was subjected to freeze-grinding and trifluoroacetyl derivatization reaction, and the epoxy modification rate was measured for each derivatized product by 1 H NMR measurement.
  • Injection stretch blow molding was performed in a wide-mouthed bottle-shaped container having a capacity of 100 ml using an injection stretch blow molding machine [manufactured by Nissei ASB Machinery Co., Ltd., ASB-12N / 10T].
  • the propylene polymer composition (PP-1) was melted at a resin temperature of 200 ° C using an injection main unit with a screw diameter of 55 mm ⁇ , and modified ethylene 'butyl alcohol was used with an injection subunit with a screw diameter of 20 mm ⁇ .
  • a polymer Karl-brand name 3-2958 ⁇ ⁇ 0 ⁇ 1—1; Epoxy modification rate 1.
  • the obtained preform was immediately transferred to the preheating zone, preheated with a kettle heater pot, preliminarily blown, and then immediately with a drawing rod and blowing air. It was stretched vertically and horizontally, stretched 1.5 times in the longitudinal direction and approximately 1.5 in the lateral direction, cooled and solidified with a blow mold, and the bottle was taken out.
  • the final dimensions of the resulting multilayer stretch blow container are approximately 180 ml of cylindrical containers with a diameter of 55.67 mm, a barrel outer diameter of 66 mm ⁇ , and a bottle height of 64 mm.
  • Table 1 shows the physical properties of the obtained multilayer stretch blow container.
  • a multilayer stretch blow container was produced in the same manner as in Example 1 except that the proportion of EVOH-1 forming the intermediate layer in the preform was changed to 18 wt%. Table 1 shows the physical properties of the resulting multilayer stretch blow container.
  • Example 3
  • Example 1 The EVOH-1 used in Example 1 was changed to a modified ethylene butyl alcohol copolymer (trade name SP434A manufactured by Kuraray Co., Ltd .; EVOH-2; epoxy modification rate 1 ⁇ 2 mol%).
  • a multilayer stretch blow container was produced in the same manner as in Example 1 except that the co-injection was carried out so that the proportion of EVOH-2 was 18% by weight.
  • the physical properties of the obtained multilayer stretch blow container are shown in Table 1.
  • Example 5 A multilayer stretch blow container was produced in the same manner as in Example 1 except that PP-4 was used instead of PP-1 in Example 1.
  • the physical properties of the obtained multilayer stretch blow container are shown in Table 1.
  • Example 5 using an ethylene'propylene polymer (PP-3) produced with a meta-orthocene catalyst is equivalent to the multilayer stretch blow container obtained in Examples 1 and 3. It can be seen that a multi-layer stretch blow container excellent in transparency as compared with the multi-layer stretch pro container obtained in Examples 1 and 3 is obtained while maintaining a high gas barrier property.
  • Example 1 The same as in Example 1 except that EVOH-1 used in Example 1 was changed to a modified ethylene-bulol alcohol copolymer (trade name SP292B; EVOH-3; epoxy modification rate 1.4 mol%, manufactured by Kuraray Co., Ltd.). Thus, a multilayer stretch blow container was produced. Table 1 shows the physical properties of the resulting multilayer stretch blow container.
  • Example 1 Same as in Example 1 except that EVOH-1 used in Example 1 was changed to a modified ethylene-butalcohol copolymer (trade name SP482B manufactured by Kuraray Co., Ltd .; EVOH-4; epoxy modification rate 1.3 mol%). Thus, a multilayer stretch blow container was produced. Table 1 shows the physical properties of the resulting multilayer stretch blow container.
  • Example 1 instead of the propylene-based polymer composition (PP-1) used in Example 1, 88.9 wt% of the polypropylene product name J246M manufactured by Prime Polymer Co., Ltd. and the product name carder QE800 manufactured by Mitsui Chemicals, Inc. were used. 11.
  • a multilayer stretch blow container was produced in the same manner as in Example 1 except that the propylene polymer composition changed to 1% by weight was used. Table 1 shows the physical properties of the resulting multilayer stretch blow container.
  • a multilayer stretch blow container was produced in the same manner as in Example 1 except that the polypropylene product name J246M manufactured by Prime Polymer was used instead of the propylene polymer composition (PP-1) used in Example 1. .
  • the physical properties of the obtained multilayer stretch blow container are shown in Table 1.
  • Example 1 In place of the modified ethylene 'butyl alcohol copolymer (trade name SP295B; EVOH-1 manufactured by Kuraray Co., Ltd.) used in Example 1, an unmodified ethylene butyl alcohol copolymer (polymer) The same procedure as in Example 1 was carried out except that Lare trade name G156B; EVOH-6) was used. The physical properties of the obtained multilayer stretch blow container are shown in Table 1.
  • Example 1 The modified ethylene ethylene glycol alcohol copolymer (trade name: SP295B; EVOH-1 manufactured by Kuraray Co., Ltd.) used in Example 1 was used in place of the unmodified ethylene.butyl alcohol copolymer (trade name: E105A manufactured by Kuraray Co., Ltd.). The same procedure as in Example 1 was carried out except that EVOH-5) was used.
  • Table 1 The physical properties of the obtained multilayer stretch blow container are shown in Table 1.
  • the multi-layer stretched hollow body (multi-layer stretch blow container) of the present invention is transparent and moldable for the first time by a three-component polymer system with a specific limited composition range. It can be seen that this is a multi-layer stretch blow container that makes full use of technology that is superior in inventive step, and that can exhibit gas barrier properties and cannot be achieved by conventional technology alone. Further, the multi-layer stretched hollow body (multi-layer stretch blow container) of the present invention is a very useful container because it is much lighter than glass and does not cause any injuries when broken.
  • the propylene-based polymer, modified propylene-based polymer, and modified ethylene′-bulu compound copolymer used in the present invention take into account all melting points, crystallization, and fluidity, and are excellent in stretchability during stretch molding. Since it is excellent, it can be stretch-molded over a wide temperature range, and the resulting container has little uneven thickness.
  • the multilayer stretched hollow body of the present invention is lightweight and transparent and has gas barrier properties, and can be suitably used for containers for foods, seasonings, drinking water, cosmetics and the like by taking advantage of the characteristics.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un matériau creux étiré multicouche ayant une excellente transparence et une excellente propriété de barrière contre les gaz. Le matériau creux étiré multicouche comprend: deux couches de surface, chacune comprenant une composition de polymère de propylène contenant un polymère de propylène (dans une quantité A en poids) et un polymère de propylène modifié par greffe avec un acide carboxylique insaturé ou un dérivé de ce type de substance (dans une quantité B en poids) (pourvu que les quantités A et B satisfont à l'exigence représentée par la formule : B/(A+B) ≥ 0.15); et une couche intermédiaire comprenant un copolymère à composé vinyle - éthylène modifié ayant un indice de fluidité à l'état fondu (ASTM D1238, 210˚C, 2.16 kg de charge) de 8 g/10 min. ou supérieur et une température de cristallisation (Tc) de 138˚C ou supérieure, la quantité (C; en poids) du copolymère à composé vinyle - éthylène dans le matériau creux étiré multicouche satisfaisant à l'exigence représentée par la formule suivante : C/(A+B+C) ≥ 0.05.
PCT/JP2007/067232 2006-09-05 2007-09-04 Matériau creux étiré multicouche WO2008029809A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
KR1020097006945A KR101029438B1 (ko) 2006-09-05 2007-09-04 다층 연신 중공체
CN2007800329661A CN101511591B (zh) 2006-09-05 2007-09-04 多层拉伸中空体
AU2007292139A AU2007292139B2 (en) 2006-09-05 2007-09-04 Multilayered stretched hollow material
US12/310,671 US20090269528A1 (en) 2006-09-05 2007-09-04 Multilayered stretched hollow material
JP2008533167A JP4844852B2 (ja) 2006-09-05 2007-09-04 多層延伸中空体

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2006240382 2006-09-05
JP2006-240382 2006-09-05
JP2006-280710 2006-10-13
JP2006280710 2006-10-13
JP2006352984 2006-12-27
JP2006-352984 2006-12-27

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US (1) US20090269528A1 (fr)
JP (1) JP4844852B2 (fr)
KR (1) KR101029438B1 (fr)
CN (1) CN101511591B (fr)
AU (1) AU2007292139B2 (fr)
WO (1) WO2008029809A1 (fr)

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EP2155389A1 (fr) * 2007-05-18 2010-02-24 Fina Technology, Inc. Catalyseurs au métallocène supportés
WO2013069426A1 (fr) * 2011-11-09 2013-05-16 株式会社資生堂 Procédé de fabrication de récipient et récipient
US8797713B2 (en) 2011-08-02 2014-08-05 Murata Manufacturing Co., Ltd. Laminated ceramic capacitor
JP2016097641A (ja) * 2014-11-26 2016-05-30 三井化学東セロ株式会社 半導体ウェハ保護シート
JP2019059860A (ja) * 2017-09-27 2019-04-18 豊田合成株式会社 ポリプロピレン樹脂組成物及び燃料電池セル用のシール部材

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US8299188B2 (en) * 2007-05-18 2012-10-30 Fina Technology, Inc. Supported metallocene catalysts
JP5615750B2 (ja) * 2011-03-29 2014-10-29 株式会社クラレ 被覆金属体及びその製造方法
CA3017353A1 (fr) * 2016-03-11 2017-09-14 Ring Container Technologies, Llc Procede de fabrication d'un recipient

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JPS60198237A (ja) * 1984-03-22 1985-10-07 三井東圧化学株式会社 ポリプロピレン系樹脂積層二軸延伸容器
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EP2155389A1 (fr) * 2007-05-18 2010-02-24 Fina Technology, Inc. Catalyseurs au métallocène supportés
EP2155389A4 (fr) * 2007-05-18 2012-06-27 Fina Technology Catalyseurs au métallocène supportés
US8797713B2 (en) 2011-08-02 2014-08-05 Murata Manufacturing Co., Ltd. Laminated ceramic capacitor
WO2013069426A1 (fr) * 2011-11-09 2013-05-16 株式会社資生堂 Procédé de fabrication de récipient et récipient
JP2013099903A (ja) * 2011-11-09 2013-05-23 Shiseido Co Ltd 透明ボトルの製造方法及び透明ボトル
JP2016097641A (ja) * 2014-11-26 2016-05-30 三井化学東セロ株式会社 半導体ウェハ保護シート
JP2019059860A (ja) * 2017-09-27 2019-04-18 豊田合成株式会社 ポリプロピレン樹脂組成物及び燃料電池セル用のシール部材

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KR20090050106A (ko) 2009-05-19
CN101511591A (zh) 2009-08-19
KR101029438B1 (ko) 2011-04-14
AU2007292139B2 (en) 2010-06-17
US20090269528A1 (en) 2009-10-29
JPWO2008029809A1 (ja) 2010-01-21
CN101511591B (zh) 2012-07-25
AU2007292139A1 (en) 2008-03-13
JP4844852B2 (ja) 2011-12-28

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